This article explores applications of total reflection x-ray fluorescence (TRXRF) to GaAs processes. The applications include determination of surface contamination and InGaAs layer thicknesses. Surface contamination can deteriorate device performance and can occur in starting substrates and in subsequent processing. We demonstrate that TRXRF is a quick, nondestructive method for identifying sulfur contamination on incoming wafers and low levels of metallic impurities from device fabrication. Variable angle TRXRF has been used to determine heterostmeture film thickness, measuring films of InGaAs on GaAs as thin as 4 nm.